TWI520973B - Composition for electrical and electronic component materials and cured product thereof - Google Patents

Description

Composition for electrical and electronic component materials and cured product thereof

The present invention relates to a composition for electrical and electronic component materials and electrical and electronic component materials. More specifically, the present invention relates to a vinyl-based polymer having a (meth)acrylonitrile group, a vinyl monomer having a (meth)acrylonyl group, and a starter, and the composition It is a composition for electrical and electronic component materials which is excellent in electrical insulation and electrode discoloration under high temperature and high humidity conditions, and an electrical and electronic component material which is obtained by curing the composition. .

Various curable resins are used as compositions for electrical and electronic component materials for a wide range of applications. For example, resin for semiconductor sealing, impregnating resin for rotation, varnish for insulation, insulating material for printed wiring board, impregnating resin for printed wiring board, coating agent for electronic components, use of conformal coating, potting agent for electronic components An epoxy resin, a quinone imine resin, an amidoxime resin, an unsaturated polyester resin, or a curable resin such as a phenol resin is used for applications such as an adhesive for electric and electronic components and a compound for heat dissipation of electronic components. However, the hardened materials of the resins are hard, and there are problems such as the occurrence of defects such as breakage of the wiring due to the difference in the coefficient of linear expansion. As a polymer which provides a rubbery curable resin without such a problem, it is known that it has a hydroxyl group or a hydrolyzable group bonded to a ruthenium atom, and at least one can be crosslinked by forming a ruthenium bond. A polyfluorene-based polymer, a polyether-based polymer, a hydrocarbon-based polymer, or a vinyl-based polymer which is a polymer of a ruthenium-based group (hereinafter also referred to as a crosslinkable decyl group). However, since the curing of these polymers utilizes a condensation reaction of a crosslinkable alkylene group, it is not necessarily required to be heated during curing, but has a common problem such as a slow curing rate and insufficient deep curing property.

As a person who does not have such problems, a polyoxane type, a polyether type, and a hydrocarbon type are disclosed. The polyoxane-based low molecular weight polyoxane compound present in the cured product causes problems in electrical characteristics such as electrical contact failure (see Patent Document 1), and the polyether-based and unsaturated hydrocarbon-based products have poor heat resistance and are saturated. Hydrocarbons are problematic in terms of handling because the resin itself has a high viscosity. The present inventors have reported that a vinyl polymer having a main chain obtained by living radical polymerization and having a (meth)acryl fluorenyl group at its terminal (Patent Documents 2 to 4) is indicated. Although the cured product is excellent in heat resistance and oil resistance, on the other hand, there is a problem in electrical insulation and electrode discoloration resistance, and it is not possible to be used for sealing of an electric component or an adhesive application.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 08-272208

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-72816

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2000-95826

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2007-77182

An object of the present invention is to provide a composition for electrical and electronic component materials having low viscosity and quick-curing properties, and a cured product which is excellent in electrical insulating properties and electrode discoloration in addition to heat resistance.

In view of the above-mentioned state, the inventors of the present invention have considered the use of a hydrophobic compound containing a long-chain aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group, etc., in order to improve the electrical insulating properties and the electrode discoloration resistance. It is known that if the moisture in the air contacts the electrode metal (copper, silver, tin, lead, nickel, gold, solder, etc.), ion migration occurs, and the electrode metal discolors and short-circuits. That is, it is considered that the cured product has low hygroscopicity by using a hydrophobic compound. As a method of using a hydrophobic compound, first, a method of copolymerizing a vinyl polymer itself with a vinyl monomer having a hydrophobic hydrocarbon group is considered, but it is feared that it is difficult to cause an unreacted high boiling point ethylene having a hydrocarbon group after the polymerization reaction. The monomer is devolatized, or the viscosity of the obtained vinyl monomer is high, and the viscosity of the curable composition is increased, so that the handleability is poor. On the other hand, in the method of blending a vinyl monomer having a hydrophobic hydrocarbon group in a curable composition, it is easy to make the curable composition have a low viscosity, and therefore workability is good by combining a vinyl monomer. The substituent structure or a plurality of vinyl monomers can easily control the hardenability, and the obtained cured product can achieve electrical insulation and electrode discoloration, thereby completing the present invention. That is, the present invention relates to the following composition for an electric and electronic component material and a cured product thereof.

The present invention relates to a composition for electrical and electronic component materials, characterized in that: (A) has at least one or more formulas (1): -OC(O)C(R ^a ) = per molecule at the molecular end. CH ₂ (1) (wherein, R ^a represents a hydrogen atom or a (meth) propylene group-based vinyl polymer represented by an organic group having a carbon number of 1 to 20, and (B) has a formula (2) ): R ^b -(OC(O)C(R ^a )=CH ₂ ) _n (2) (wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ^b represents a carbon number of 6 to 20 The organic group, n represents a (meth)acryloyl group-based vinyl monomer represented by an integer of 2 to 6, and (C) a starter, and is relative to the component (A) and the component (B) The total amount is 100% by weight, and the component (B) is contained in an amount of 25% by weight or more and 45% by weight or less.

The present invention relates to a composition for an electrical and electronic component material comprising: (A) having at least one or more formula (1): -OC(O)C(R ^a )=CH ₂ per molecule at the molecular terminal (1) (wherein, R ^a represents a hydrogen polymer or a (meth)acryloyl group-based vinyl polymer represented by an organic group having 1 to 20 carbon atoms; and (B) has a formula (2): R ^b -(OC(O)C(R ^a )=CH ₂ ) _n (2) (wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ^b represents an organic group having 6 to 20 carbon atoms; a group (n) represents a (meth)acryloyl group-based vinyl monomer represented by an integer of 2 to 6, and (D) has a formula (3): R ^c -OC(O)C(R ^a ) =CH ₂ (3) (wherein, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ^c represents an organic group having 6 to 20 carbon atoms) (meth)acryloyl group The vinyl monomer and the (C) initiator are 100 weight% of the total of the component (B) and the component (D), and the total of the component (B) and the component (D) is 25 weight. % or more and 65% by weight or less, and contains 5% by weight or more of the component (B).

It is preferably 100% by weight based on the total of the components (A), (B) and (D), and the total of the components (B) and (D) is 30% by weight or more and 55% by weight or less, and 15% by weight. More than or equal to the component (B).

The amount of the component (C) is preferably 0.001 to 10 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (D).

It is preferred that the main chain of the component (A) is produced by polymerizing an acrylate monomer.

It is preferred that the main chain of the component (A) is produced by a living radical polymerization method, more preferably by an atom transfer radical polymerization method.

It is preferred that the main chain of the component (A) is produced by polymerization of a vinyl monomer using a chain transfer agent.

It is preferred that the component (A) has a number average molecular weight of 3,000 or more.

The ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography of the ethylene-based polymer of the component (A) is preferably less than 1.8.

It is preferred that the component (B) is a vinyl monomer having two (meth)acrylonyl groups in one molecule.

Preferably, the component (C) is a photoradical initiator.

The present invention relates to a composition for an electric or electronic component material in which the composition for an electric or electronic component material described above is brought into contact with an electrode metal.

The present invention relates to an electrical and electronic component material obtained by curing the composition for electrical and electronic component materials described above.

The present invention relates to a cured product obtained by curing the above-described composition for an electric or electronic component material by an active energy ray or heat.

The present invention provides a composition for electrical and electronic component materials having low viscosity and quick-curing properties, and a cured product excellent in electrical insulating properties and electrode discoloration in addition to heat resistance.

Hereinafter, the curable composition of the present invention will be described in detail.

<<(A) component>>

The component (A) in the present invention means having at least one or more formula (1): -OC(O)C(R ^a )=CH ₂ (1) per molecule at the molecular terminal (wherein R ^a A (meth)acryloyl group-based vinyl polymer represented by a hydrogen atom or an organic group having 1 to 20 carbon atoms.

When the component (A) is produced, the reaction may not be reacted or a side reaction may occur. Therefore, the average value of the (meth)acrylonyl group introduced into the ethylene-based polymer may be deviated from the setting. In the present invention, when the average value of the (meth)acrylinyl group introduced into the terminal of the ethylene-based polymer is 0.8 or more, the mixture is referred to as the component (A).

The average value of the (meth)acrylinyl group introduced into the ethylene-based polymer is preferably 0.8 or more and 2.3 or less, more preferably 1.5 or more and 2.5 or less, and still more preferably 1.8 or more. 2.2 or less. When the number is less than 0.8, the unreacted components of the cured product increase, and thus heat resistance and mechanical properties may be lowered. In the case of more than 3.0, the crosslinking point of the cured product increases, so that the elongation of the cured product may decrease and cracks may easily occur.

Further, one or more (meth)acrylinyl groups introduced into the ethylene-based polymer are present at the molecular terminal, but the position of the other (meth)acryl-based group is not particularly limited. In terms of increasing the distance between the crosslinking points and improving the elongation property of the cured product, it is preferably a form close to the end side of the other molecule, and particularly preferably a form at the end of the other molecule. In other words, the (meth)acrylinyl group introduced into the vinyl polymer is at least one or more at the molecular end per molecule, and preferably two at both ends of the molecule.

R ^a in the (meth)acrylonyl group is ^a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. The organic group means a group shown below.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a nitrile group, and the like. A substituent such as a hydroxyl group.

Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a decyl group.

Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group.

Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenylethyl group.

Preferred examples of R ^a include -H, -CH ₃ , -CH ₂ CH ₃ , -(CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), -C ₆ H ₅ , -CH ₂ OH, -CN, etc., preferably -H, -CH ₃ .

The vinyl monomer constituting the main chain of the component (A) is not particularly limited, and various types can be used. As an example, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (methyl) ) n-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate , n-heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, (A) Isodecyl acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentyl (meth) acrylate, (meth) acrylate Alkyl ester, phenyl (meth) acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-(meth) acrylate Methoxybutyl ester, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, (methyl) ) glycidyl acrylate, (meth) propyl 2-Aminoethyl olefin, γ-(methacryloxypropyl)trimethoxynonane, ethylene oxide adduct of (meth)acrylic acid, trifluoromethyl (meth)acrylate Ester, 2-trifluoromethylethyl (meth)acrylate, 2-perfluoroethylethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate , 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate, diperfluoromethyl methyl (meth)acrylate, 2-perfluoromethyl-2-(meth)acrylate Perfluoroethyl ethyl ester, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, etc. (meth)acrylic monomer; aromatic vinyl monomer such as styrene, vinyl toluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid or a salt thereof; perfluoroethylene, perfluoropropene, Fluorine-containing vinyl monomer such as vinylidene fluoride; vinyl-containing monomer such as vinyltrimethoxynonane or vinyltriethoxysilane; maleic anhydride, maleic acid, maleic acid Monoalkyl esters and dialkyl esters; fumaric acid, antibutene Monoalkyl and dialkyl esters of acid; maleimide, methyl maleimide, ethyl maleimide, propyl maleimide, Butyl maleimide, hexyl maleimide, octyl maleimide, dodecyl maleimide, octadecyl maleimide, benzene a maleimide-based monomer such as cis-butenylenediamine or cyclohexylmethyleneimine; a vinyl-containing monomer such as acrylonitrile or methacrylonitrile; acrylamide a vinyl monomer containing a guanamine group such as methacrylamide; a vinyl ester such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate or vinyl cinnamate; ethylene, propylene, etc. Olefins; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and the like. These may be used singly or in combination of plural kinds.

Among them, an aromatic vinyl monomer and a (meth)acrylic monomer are preferable in terms of physical properties of the product and the like. More preferably, it is an acrylate type monomer and a methacrylate type monomer, More preferably, it is butyl acrylate, ethyl acrylate, 2-methoxyethyl acrylate.

In terms of heat resistance, the vinyl monomer constituting the main chain is particularly preferably butyl acrylate.

The vinyl monomer constituting the main chain is particularly preferably butyl acrylate or 2-methoxyethyl acrylate in terms of water absorption resistance and moisture absorption resistance.

In the present invention, the preferred monomers may be copolymerized with the other monomers. In this case, it is preferred to contain 40% by weight or more of the preferred monomers. Further, in the above expressions, for example, (meth)acrylic acid means acrylic acid and/or methacrylic acid.

The molecular weight distribution of the component (A) [the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is not particularly limited, and preferably is not 1.8 is more preferably 1.5 or less, further preferably 1.3 or less. Further, in the GPC measurement in the present invention, chloroform or tetrahydrofuran is usually used as a mobile phase, and a polystyrene gel column is used, and the molecular weight value is determined in terms of polystyrene.

The number average molecular weight of the ethylene-based polymer (A) in the present invention is not particularly limited, but is preferably 3,000 to 100,000, more preferably 5,000 to 80,000, still more preferably 8,000 to 50,000, as measured by GPC. . When the molecular weight is too low, the original properties of the ethylene-based polymer (A) tend not to be exhibited. On the other hand, if the molecular weight is too high, handling tends to be difficult.

<Synthesis of ethylene-based polymer (A)>

The vinyl polymer (A) used in the present invention can be obtained by various polymerization methods, and is not particularly limited. However, in terms of versatility of the monomer, ease of control, and the like, a radical polymerization method is preferred. In the radical polymerization, it is more preferable to control radical polymerization. The controlled radical polymerization method can be classified into a "chain transfer agent method" and a "living radical polymerization method". Further, it is preferably a living radical polymerization which is easy to control the molecular weight and molecular weight distribution of the obtained ethylene-based polymer (A), and is particularly preferable in terms of availability of a raw material and ease of introduction of a functional group to a polymer terminal. Free radical polymerization for atom transfer. The radical polymerization, the controlled radical polymerization, the chain transfer agent method, the living radical polymerization method, and the atom transfer radical polymerization are known polymerization methods. For each of the polymerization methods, for example, Japanese Patent Laid-Open Publication No. 2005-232419 Or Japanese Patent Laid-Open Publication No. 2006-291073, and the like.

Hereinafter, one of the preferred synthesis methods of the ethylene-based polymer (A) in the present invention, that is, atom transfer radical polymerization will be briefly described.

In the atom transfer radical polymerization, it is preferred to use an organic halide, especially an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a halogen having a benzyl group). A compound), or a sulfonium halide compound or the like is used as a starter. Specifically, a compound described in paragraphs [0040] to [0064] of JP-A-2005-232419 can be cited.

In order to obtain a vinyl polymer having two or more functional groups in one molecule, it is preferred to use an organic halide or a sulfonium halide compound having two or more starting points as a starting agent. If it is specifically illustrated, it can be enumerated:

Wait.

The vinyl monomer used in the atom transfer radical polymerization is not particularly limited, and all of the vinyl monomers exemplified above can be preferably used.

The transition metal complex used as the polymerization catalyst is not particularly limited, and preferably, it is preferably a metal which is a central metal of Group 7, Group 8, Group 9, Group 10, or Group 11 elements of the periodic table. More preferably, the complex is a transition metal complex having a zero-valent copper, a monovalent copper, a divalent ruthenium, a divalent iron or a divalent nickel as a central metal, and particularly preferably a copper complex. When a monovalent copper compound for forming a copper complex is specifically exemplified, there are cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. . In the case of using a copper compound, in order to increase the catalytic activity, 2,2'-bipyridine or a derivative thereof, 1,10-morpholine or a derivative thereof, tetramethylethylenediamine, pentamethyldioxide are added. A polyamine such as ethylene triamine or hexamethyltris(2-aminoethyl)amine or the like is used as a ligand.

The polymerization can be carried out without a solvent or in various solvents. The type of the solvent is not particularly limited, and examples thereof include the solvents described in paragraph [0067] of JP-A-2005-232419. These may be used alone or in combination of two or more. Further, the polymerization can also be carried out in an emulsion system or a system using a supercritical fluid CO ₂ as a medium.

The polymerization temperature is not limited and can be carried out in the range of 0 to 200 ° C, preferably in the range of room temperature to 150 ° C.

<Polymerizable carbon-carbon double bond introduction method>

A known method can be used for the introduction of the polymerizable carbon-carbon double bond. For example, the method described in paragraphs [0080] to [0091] of JP-A-2004-203932 can be cited. Among these methods, in terms of easier control, it is preferred to manufacture a terminal halogen group of a vinyl polymer by a compound having a polymerizable carbon-carbon double bond.

a (meth)acrylic polymer having a terminal halogen group is a method of polymerizing a vinyl monomer by using the above organic halide or a sulfonium halide compound as a starting agent and a transition metal complex as a catalyst, or It is produced by a method in which a halide is used as a chain transfer agent to polymerize a vinyl monomer, but is preferably the former.

The compound having a polymerizable carbon-carbon double bond is not particularly limited, and a compound represented by the following formula (4), M ⁺ -OC(O)C(R)=CH ₂ (4) can be used as the above. Specific examples of R in the formula (4) include, for example, -H, -CH ₃ , -CH ₂ CH ₃ , -(CH ₂ ) _n CH ₃ (n represents an integer of 2 to 19), -C ₆ H ₅ , -CH ₂ OH, -CN, etc., preferably -H, -CH ₃ .

The counter cation of the M ⁺ -based oxyanion in the above formula (4), and the type of M ⁺ is an alkali metal ion, and specific examples thereof include lithium ion, sodium ion, potassium ion, and quaternary ammonium ion. Examples of the quaternary ammonium ion include tetramethylammonium ion, tetraethylammonium ion, tetrabenzylammonium ion, trimethyldodecyl ammonium ion, tetrabutylammonium ion, and dimethylpiperidinium ion. Etc., preferably sodium ion or potassium ion.

The amount of the oxyanion to be used in the formula (4) is preferably from 1 to 5 equivalents, more preferably from 1.0 to 1.2 equivalents, per equivalent of the halogen group.

The solvent for carrying out the reaction is not particularly limited, but in terms of the nucleophilic substitution reaction, a polar solvent is preferred, and for example, tetrahydrofuran or two can be used. Alkane, diethyl ether, acetone, dimethyl hydrazine, dimethylformamide, dimethylacetamide, hexamethylphosphoric acid triamine, acetonitrile, and the like.

The temperature at which the reaction is carried out is not limited, and it is usually carried out at 0 to 150 ° C to maintain the polymerizable terminal group, preferably at room temperature to 100 ° C.

<<(B) component>>

The component (B) of the present invention has the formula (2): R ^b -(OC(O)C(R ^a )=CH ₂ ) _n (2) (wherein R ^a represents a hydrogen atom or a carbon number of 1~ a vinyl monomer having 20 (organic group, R ^b represents an organic group having 6 to 20 carbon atoms, and n is an integer of 2 to 6), and is a component of (A) and B) The mixture of the components contains 25% by weight or more and 45% by weight or less. The n of the formula (2) is preferably 3 or less, and more preferably 2, in terms of excellent mechanical properties (elongation and strength) of the cured product.

R ^a may be the same above general formula (1) of R ^a.

R ^{b is} preferably an organic group having 6 to 20 carbon atoms, more preferably an organic group having 8 to 18 carbon atoms, and more preferably an organic group having 12 to 15 carbon atoms. When the carbon number is less than 6, the component (B) tends to be volatile and the weight change at a high temperature tends to increase. On the other hand, when the carbon number is more than 20, the component (B) tends to have a high viscosity, and the effect of lowering the viscosity of the composition tends to be lowered.

R ^{b is} preferably a chain aliphatic structure, and preferably has a carbon number of 8 or more, more preferably in terms of good mechanical properties (elongation and strength) of the cured product and excellent water absorption resistance and moisture absorption resistance. The carbon number is 12 or more.

Specific examples of the component (B) having a chain aliphatic structure include triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and 3-methyl-1,5- Pentandiol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di Methyl) acrylate, 2-methyl-1,8-octanediol di(meth) acrylate, 1,9-nonanediol di(meth) acrylate, 1,10-decanediol di Methyl) acrylate or the like. Further, a compound represented by the following formula or the like can also be mentioned.

CH ₂ =CHC(O)O-(CH ₂ ) _n -OC(O)CH=CH ₂

(n is an integer from 6 to 20)

CH ₂ =C(CH ₃ )C(O)O-(CH ₂ ) _n -OC(O)C(CH ₃ )=CH ₂

(n is an integer from 6 to 20)

CH ₂ =CHC(O)O-(CH ₂ CH ₂ O) _n -OC(O)CH=CH ₂

(n is an integer from 3 to 10)

CH ₂ =C(CH ₃ )C(O)O-(CH ₂ CH ₂ O) _n -OC(O)C(CH ₃ )=CH ₂

(n is an integer from 3 to 10)

The component (B) having a chain aliphatic structure is preferably a vinyl monomer having no ether structure in terms of good heat resistance and insulation properties.

Examples of the vinyl monomer having no ether structure include 3-methyl-1,5-pentanediol di(meth)acrylate and 1,6-hexanediol di(meth)acrylate. , 7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 1 , 9-nonanediol di(meth)acrylate, 1,10-nonanediol di(meth)acrylate, and the like.

R ^{b is} preferably a cyclic structure, more preferably an alicyclic aliphatic structure, and more preferably a polycyclic aliphatic structure, in terms of excellent water absorption resistance and moisture absorption resistance of the cured product.

Specific examples of the component (B) having an alicyclic aliphatic structure include cyclohexane dimethanol di(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, and 1 , 3-adamantane dimethanol di(meth)acrylate, and the like. As a component (B) which is particularly excellent in balance of water absorption resistance, moisture absorption resistance, low volatility, and low viscosity, 1,9-nonanediol diacrylate and 1,10-nonanediol diacrylate are mentioned. , dimethylol tricyclodecane diacrylate.

The vinyl monomer having 3 to 6 (meth) acrylonitrile groups is not particularly limited, but is preferably a trimethylol group in terms of low viscosity, high reactivity, and good availability. Propane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, bis(trimethylol)propane tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(methyl) )Acrylate.

The component (B) may be used in combination of two or more kinds.

The amount of the component (B) to be added is 25% by weight or more and 45% by weight or less, more preferably 30% by weight or more and 40% by weight or less based on 100% by weight of the total of the components (A) and (B). When the amount of the component (B) added is less than 25% by weight, the effect of resistance to electrode discoloration and low viscosity is lowered. On the other hand, when the amount of the component (B) added is more than 45% by weight, the mechanical properties (elongation, strength) of the cured product are lowered.

<<(D) component>>

The component (D) of the present invention has the formula (3): R ^c -OC(O)C(R ^a )=CH ₂ (3) (wherein R ^a represents a hydrogen atom or an organic group having a carbon number of 1 to 20 a vinyl monomer having a (meth)acrylonyl group represented by a group (R ^c represents an organic group having 6 to 20 carbon atoms), and a total of (A) component, (B) component, and (D) component 100% by weight, the total of the component (B) and the component (D) is 25% by weight or more and 65% by weight or less, and the component (B) is contained in an amount of 5% by weight or more. R ^{a of the} above formula (1) can be similarly used for R ^a .

R ^{c is} preferably an organic group having 6 to 20 carbon atoms, more preferably an organic group having 8 to 18 carbon atoms, and more preferably an organic group having 12 to 15 carbon atoms. When the carbon number is less than 6, the component (D) tends to be volatile and the weight change at a high temperature tends to increase. On the other hand, when the carbon number is more than 20, the component (D) tends to have a high viscosity, and the effect of lowering the viscosity of the composition tends to be lowered.

R ^{c is} preferably a chain aliphatic structure, and preferably has a carbon number of 8 or more, more preferably in terms of good mechanical properties (elongation and strength) of the cured product and excellent water absorption resistance and moisture absorption resistance. The carbon number is 12 or more. Specific examples of the component (D) having a chain aliphatic structure include n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, and (meth)acrylic acid. Isooctyl ester, 2-ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate An ester, n-dodecyl (meth)acrylate, tridecyl (meth)acrylate, octadecyl (meth)acrylate, isostearyl (meth)acrylate, and the like. Further, a compound represented by the following formula or the like can also be mentioned.

CH ₂ =CHC(O)O-(CH ₂ ) _n -CH ₃

(n is an integer from 5 to 19)

CH ₂ =C(CH ₃ )C(O)O-(CH ₂ ) _n -CH ₃

(n is an integer from 5 to 19)

CH ₂ =CHC(O)O-(CH ₂ CH ₂ O) _n -CH ₃

(n is an integer from 3 to 9)

CH ₂ =C(CH ₃ )C(O)O-(CH ₂ CH ₂ O) _n -CH ₃

(n is an integer from 3 to 9)

CH ₂ =CHC(O)O-(CH ₂ CH ₂ O) _n -CH ₂ CH ₃

(n is an integer from 2 to 9)

CH ₂ =C(CH ₃ )C(O)O-(CH ₂ CH ₂ O) _n -CH ₂ CH ₃

(n is an integer from 2 to 9)

The component (D) having a chain aliphatic structure is preferably a vinyl monomer having no ether structure in terms of good heat resistance and insulation properties. Examples of the vinyl monomer having no ether structure include n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, and isooctyl (meth)acrylate. 2-ethylhexyl methacrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, (methyl) N-dodecyl acrylate, tridecyl (meth) acrylate, octadecyl (meth) acrylate, isostearyl (meth) acrylate, and the like.

R ^{c is} preferably a cyclic structure, more preferably an alicyclic aliphatic structure, and more preferably a polycyclic aliphatic structure, in terms of excellent water absorption resistance and moisture absorption resistance of the cured product.

Specific examples of the component (D) having an alicyclic aliphatic structure include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and 3,3,5-trimethylcyclohexane. (Meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyl (meth)acrylate Oxyethyl ester, 1-adamantyl (meth)acrylate, tricyclopentyl (meth)acrylate, tricyclopentenyl (meth)acrylate, N-(methyl)propenyl-ε- Caprolactam, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-ethyl-3-oxetanyl (meth)acrylate.

Specific examples of the component (D) having a polycyclic aliphatic structure include dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and (meth)acrylic acid. Dicyclopentyl ester, dicyclopentyloxyethyl (meth)acrylate, 1-adamantyl (meth)acrylate, tricyclopentanyl (meth)acrylate, tricyclopentenyl (meth)acrylate .

Specific examples of the component (D) having a cyclic structure other than the alicyclic aliphatic structure include phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, and toluene (meth)acrylate. Formyl ester, benzyl (meth) acrylate, nonyl phenoxy polyethylene glycol (meth) acrylate, O-phenyl phenol (meth) acrylate. Examples of the component (D) excellent in balance of water absorption resistance, moisture absorption resistance, low volatility, and low viscosity effect include isodecyl acrylate, isodecyl acrylate, n-dodecyl acrylate, and acrylic acid. Alkyl ester, isobornyl acrylate, dicyclopentanyl acrylate.

The component (D) may be used in combination of two or more kinds.

The component (D) is preferably used in combination with the component (B) in terms of improving the mechanical properties (elongation and strength) of the cured product and obtaining the effects of electrical insulation, electrode discoloration, and low viscosity. .

The amount of addition of the component (B) and the component (D) is 100% by weight based on the total of the components (A), (B) and (D), and the components (B) and (D) The total amount is preferably 25% by weight or more and 65% by weight or less, and the component (B) is 5% by weight or more, and preferably the total of the components (B) and (D) is 30% by weight or more and 55% by weight or less, and B) The component is 5% by weight or more, and more preferably the total of the component (B) and the component (D) is 35 wt% or more and 45 wt% or less, and the component (B) is 5% by weight or more.

When the amount of the component (B) and the component (D) is less than 25% by weight, the effect of resistance to electrode discoloration and low viscosity is lowered. On the other hand, when the amount of the component (B) and the component (D) is more than 65% by weight, the mechanical properties (elongation, strength) of the cured product are lowered, or the viscosity is enhanced, or the heat resistance is lowered. Happening.

In addition, the amount of the component (B) added in the case where the component (B) and the component (D) are used in combination is 5% by weight or more, preferably 10% by weight or more, and more preferably 15% by weight or more. When the amount of the component (B) added is less than 5% by weight, the effect of resistance to electrode discoloration is lowered.

In addition, the amount of the component (B) to be used in combination with the component (B) and the component (D) described above is preferably 45% by weight or less, more preferably 40% by weight or less, and still more preferably 35% by weight. %the following. When the amount of the component (B) added is more than 45% by weight, the mechanical properties (elongation, strength) of the cured product are lowered.

<<(C) component>>

Examples of the component (C) of the present invention include a photopolymerization initiator, a thermal polymerization initiator, a redox initiator, and the like.

The photopolymerization initiator, the thermal polymerization initiator, and the redox initiator may be used singly or in combination of two or more kinds. When used in the form of a mixture, the use of each initiator The amounts are preferably within the respective ranges described below.

In the case of hardening by the active energy ray, it is not particularly limited, and a photoradical initiator and a photoanion initiator are preferred, and a photoradical initiator is particularly preferred.

Examples of the photoradical initiator include acetophenone, propiophenone, benzophenone, Xanthol, anthrone, benzaldehyde, anthracene, triphenylamine, carbazole, and 3-methylacetophenone. 4-methylacetophenone, 3-pentylacetophenone, 2,2-diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylbenzene Ethyl ketone, p-diethyl benzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4-Chloro-4'-benzylbenzophenone, 3-chlorooxazepinone, 3,9-dichlorooxazepinone, 3-chloro-8-mercaptooxaxanone, benzoin, benzoin Ether, benzoin butyl ether, bis(4-dimethylaminophenyl) ketone, benzyl methoxy copper, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenyl Ethyl-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1-[4-( Methylthio)phenyl]-2-morpholinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, two Benzoquinone and the like. Among these, as a photoradical initiator which is excellent in ultraviolet curability, an α-hydroxyketone compound (for example, benzoin, benzoin methyl ether, benzoin butyl ether, 1-hydroxy-cyclohexyl-phenyl-ketone) is preferred. Phenyl ketone derivatives (eg, acetophenone, propiophenone, benzophenone, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2, 2 -diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, 3-methoxybenzophenone, 4-methyldiphenyl Methyl ketone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4-chloro-4'-benzylbenzophenone, bis(4-dimethylaminophenyl) ) Ketone, etc.).

Further, examples of the photoradical initiator which suppresses oxygen inhibition on the surface of the cured product include 2-hydroxy-1-[4-[4-(2-) having two or more photodegradable groups in the molecule. Hydroxy-2-methyl-propenyl)-benzyl]phenyl]-2-methyl-propan-1-one (trade name: IRGACURE 127, manufactured by Ciba Japan), 1-[4-(4-benzamide) Oxyphenylthioalkyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one (trade name ESURE 1001M), methyl benzalkonate (trade name SPEEDCURE MBF, manufactured by LAMBSON), O-ethoxyimino-1-phenylpropan-1-one (trade name SPEEDCURE PDO, manufactured by LAMBSON), oligomeric [2-hydroxy-2-methyl- [4-(1-methylvinyl)phenyl]acetone (trade name: ESCURE KIP150, manufactured by LAMBERTI), and 1,2- as a hydrogen radical-type photoradical initiator having three or more aromatic rings in the molecule Octanedione, 1-[4-(phenylthio)-2-(O-benzamide)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl) -9H-carbazol-3-yl]-1-(O-acetamidine), 4-benzylidene-4'-methyldiphenyl sulfide, 4-phenylbenzophenone, 4,4 ',4"-(hexamethyltriamino)triphenylmethane.

Further, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide and bis(2,4,6-trimethylbenzylidene) which are characterized by improvement in deep hardenability are mentioned. -Phenylphosphine oxide, bis(2,6-dimethylbenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzylidene a fluorenylphosphine oxide-based photoradical initiator such as diphenyl-phosphine oxide.

Further, in terms of balance between active energy ray hardenability and storage stability of the curable composition of the present invention, 1-hydroxy-cyclohexyl-phenyl-ketone and 2-hydroxy-2-methyl group are more preferred. 1-phenyl-propan-1-one, bis(4-dimethylaminophenyl)one, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionate) ()-benzyl]phenyl]-2-methyl-propan-1-one (trade name: IRGACURE 127, manufactured by Ciba Japan), 1-[4-(4-benzylideneoxyphenylsulfanyl)benzene 2-methyl-2-(4-methylphenylsulfonyl)propan-1-one (trade name: ESURE 1001M), methyl benzalkonate (trade name SPEEDCURE MBF, manufactured by LAMBSON) , O-ethoxyimino-1-phenylpropan-1-one (trade name SPEEDCURE PDO, manufactured by LAMBSON), oligomeric [2-hydroxy-2-methyl-[4-(1-methylethylene) Phenyl]acetone (trade name ESCURE KIP150, manufactured by LAMBERTI), 1,2-octanedione, 1-[4-(phenylthio)-2-(O-benzamide), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazol-3-yl]-1-(O-acetamidine), 4-benzylidene-4' -methyldiphenyl sulfide, 4-phenylbenzophenone, 4,4',4"-(hexamethyltriamino)triphenylmethane, 2,4,6-trimethylbenzylidene -diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethylbenzylidene)-2,4,4 - Trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide.

As the near-infrared photopolymerization initiator, a near-infrared light absorbing cationic dye or the like can be used. The near-infrared light absorbing cationic dye is preferably used in the vicinity of the light source of 650 to 1500 nm, and is disclosed in, for example, Japanese Patent Laid-Open No. Hei. No. Hei. The infrared light absorbing cationic dye-borate anion complex or the like is further preferably a boron-based sensitizer.

These photopolymerization initiators may be used singly or in combination of two or more kinds, or may be used in combination with other compounds.

Specific examples of the combination with other compounds for improving the curability include a combination with an amine such as diethanolmethylamine, dimethylethanolamine or triethanolamine, and further, an iodine such as diphenylphosphonium chloride or the like is combined therein. Salt, combined with pigments and amines such as methylene blue.

Further, in the case of using the above photopolymerization initiator, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, benzoquinone or p-tert-butyl catechol may be added as needed. class.

The amount of the component (C) to be added is not particularly limited, but it is preferably 0.001 based on 100 parts by weight of the total of the components (A), (B) and (D) in terms of hardenability and storage stability. It is preferably 10 parts by weight, more preferably 0.01 to 5 parts by weight.

The thermal polymerization initiator is not particularly limited, and examples thereof include an azo initiator, a peroxide initiator, and a persulfate initiator. The azo-based initiator is not limited, and examples thereof include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (VAZO33) and 2,2'-couple. Nitrogen bis(2-amidinopropane) dihydrochloride (VAZO50), 2,2'-azobis(2,4-dimethylvaleronitrile) (VAZO52), 2,2'-azobis (iso) Butyronitrile) (VAZO64), 2,2'-azobis-2-methylbutyronitrile (VAZO67), 1,1-azobis(1-cyclohexanecarbonitrile) (VAZO88) (all available from DuPont Chemical Obtained, 2,2'-azobis(2-cyclopropylpropionitrile), and 2,2'-azobis(methylisobutyrate) (V-601) (obtained from Wako Pure Chemicals) )Wait.

The peroxide initiator is not limited, and examples thereof include benzammonium peroxide, ruthenium peroxide, laurel peroxide, ruthenium peroxide, dicetyl peroxydicarbonate, and di(4- Tert-butylcyclohexyl peroxydicarbonate (Perkadox 16S) (available from Akzo Nobel), di(2-ethylhexyl)peroxydicarbonate, tert-butyl peroxypivalate (Lupersol 11) (available from Elf Atochem), tributyl acrylate (2-ethylhexanoic acid) (Trigonox 21-C50) (available from Akzo Nobel), and dicumyl peroxide.

The persulfate initiator is not limited, and examples thereof include potassium persulfate, sodium persulfate, and ammonium persulfate.

A preferred thermal polymerization initiator is selected from the group consisting of azo initiators and peroxide initiators. Further preferred are 2,2'-azobis(methyl isobutyrate), t-butyl peroxypivalate, bis(4-t-butylcyclohexyl)peroxydicarbonate, And mixtures of such.

The thermal polymerization initiator may be used singly or in combination of two or more.

In the case where a thermal polymerization initiator is used as the component (C), the thermal polymerization initiator is present as a catalyst in an effective amount, and the amount thereof is not particularly limited, but is relative to the component (A) of the present invention. The total of 100 parts by weight of the component (B) and the component (D) is preferably 0.01 to 5 parts by weight, more preferably 0.025 to 2 parts by weight.

Redox initiators can be used in a wide range of temperature ranges. It is especially advantageous to use the following initiator types at normal temperatures.

The appropriate redox initiator is not limited, and examples thereof include a combination of the persulfate initiator and a reducing agent (sodium methylsulfite, sodium hydrogensulfite, etc.); an organic peroxide and three a combination of ammonium, for example, a combination of benzamidine peroxide and dimethylaniline, a combination of cumene hydroperoxide and aniline; a combination of an organic peroxide and a transition metal, for example, cumene hydroperoxide Combination with cobalt naphthenate, and the like.

As a preferred redox initiator, it is a combination of an organic peroxide and a tertiary ammonium, a combination of an organic peroxide and a transition metal, more preferably a combination of cumene hydroquinone and aniline, and hydroperoxidation. A combination of cumene and cobalt naphthenate.

The redox initiator may be used singly or in combination of two or more.

When a redox-based initiator is used as the component (C), the redox-based initiator is present as a catalyst in an effective amount, and the amount thereof is not particularly limited, and is (A) in relation to the present invention. The total amount of the component, the component (B) and the component (D) is preferably from 0.01 to 5 parts by weight, more preferably from 0.025 to 2 parts by weight, based on 100 parts by weight.

<<Sclerosing composition>>

The curable composition of the present invention contains a vinyl polymer of the component (A), a vinyl monomer of the component (B), an initiator of the component (C), and a vinyl monomer containing the component (D) as necessary. In order to adjust the physical properties, various additives such as a polymerizable monomer and/or oligomer, a hardening adjuster, a metal soap, a filler, a micro hollow particle, a plasticizer, and the like may be appropriately formulated as needed. Agent, solvent, flame retardant, antioxidant, light stabilizer, ultraviolet absorber, physical property adjuster, radical inhibitor, metal passivator, antiozonant, phosphorus peroxide decomposer, lubricant, pigment , a foaming agent, a photocurable resin, and the like. These various additives may be used singly or in combination of two or more.

Specific examples of such an additive are described in, for example, Japanese Patent Application Laid-Open No. Hei-4-69659, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. Wait.

<Polymerizable monomer and/or oligomer>

The curable composition of the present invention may contain a monomer and/or an oligomer other than the component (B) and the component (D) within the range in which the effects of the present invention are not impaired. In terms of hardenability, a monomer and/or oligomer having a radical polymerizable group is preferred.

Examples of the radical polymerizable group include a (meth)acrylinyl group such as a (meth)acryl group, a styryl group, an acrylonitrile group, a vinyl ester group, an N-vinyl pyrrolidone group, and an acrylonitrile group. An amine group, a conjugated dienyl group, a vinyl ketone group, a vinyl chloride group or the like. Among them, those having a (meth)acrylinyl group similar to the vinyl polymer used in the present invention are preferred.

Specific examples of the monomer include a (meth) acrylate monomer, a cyclic acrylate, a styrene monomer, an acrylonitrile, a vinyl ester monomer, N-vinyl pyrrolidone, and acrylamide. A monomer, a conjugated diene monomer, a vinyl ketone monomer, a halogenated ethylene-vinylidene halide monomer, a polyfunctional monomer, or the like.

Examples of the (meth)acrylate monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, and isopropyl (meth)acrylate. Base) n-butyl acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, (a) 3-methoxybutyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, 2-amine (meth) acrylate Ethyl ethyl ester, N-(methyl) propylene decylmorpholine, (meth)acrylic acid tetrahydrofuran ester, γ-(methacryloxypropyl)trimethoxydecane, (meth)acrylic acid epoxy B Alkyl adduct, propylene oxide adduct of (meth)acrylic acid, trifluoromethyl methyl (meth)acrylate, 2-trifluoromethyl ethyl (meth)acrylate, (meth)acrylic acid 2 -Perfluoroethylethyl ester, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl (meth)acrylate, perfluoromethyl (meth)acrylate , (per) fluoromethyl methyl (meth) acrylate, 2- (meth) acrylate Methyl-2-perfluoroethyl ethyl ester, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecyl (meth)acrylate Alkyl ethyl ester and the like.

Examples of the styrene-based monomer include styrene and α-methylstyrene.

Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, and vinyl butyrate.

Examples of the acrylamide-based monomer include acrylamide, N,N-dimethylacrylamide, and the like.

Examples of the conjugated diene monomer include butadiene and isoprene.

Examples of the vinyl ketone monomer include methyl vinyl ketone and the like.

Examples of the halogenated vinyl-vinylidene halide-based monomer include vinyl chloride, vinyl bromide, vinyl iodide, vinylidene chloride, and vinylidene bromide.

Examples of the polyfunctional monomer include neopentyl glycol polypropoxy di(meth)acrylate, trimethylolpropane polyethoxy (methyl) triacrylate, and bisphenol F polyethoxy di Methyl) acrylate, bisphenol A polyethoxy di(meth) acrylate, and the like.

Examples of the oligomer include a bisphenol A epoxy acrylate resin, a phenol novolak epoxy acrylate resin, a cresol novolak epoxy acrylate resin, and a COOH based modified epoxy acrylate resin. Epoxy acrylate resin; by polyol (polybutylene glycol, ethylene glycol with ethylene glycol and adipic acid, ε-caprolactone modified polyester diol, polypropylene glycol, polyethylene glycol a polycarbonate diol, a hydrogenated polyisoprene having a hydroxyl group at the terminal, a polybutadiene having a hydroxyl group at the terminal, a polyisobutylene having a hydroxyl group at the terminal, and the like, and an organic isocyanate (toluene diisocyanate, isophorone diisocyanate, A urethane resin obtained by diphenylmethane diisocyanate, hexamethylene diisocyanate, benzene dimethylene diisocyanate or the like, and a hydroxyl group-containing (meth) acrylate (hydroxy methacrylate) An urethane urethane resin obtained by reacting an ester, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, pentaerythritol triacrylate, etc.; introduced into the above polyol via an ester bond (A) Base) Resins; polyester acrylate resins, poly (meth) acrylate-based resin ((meth) acrylate resin having a polymerizable reactive group of the poly) and the like.

Among the above, a monomer and/or an oligomer having a (meth)acrylinyl group is preferred. Further, the number average molecular weight of the monomer and/or oligomer having a (meth) acrylonitrile group is preferably 5,000 or less. Further, in order to improve the surface hardenability or to lower the viscosity in order to improve the workability, when the monomer is used, the molecular weight is 1,000 or less, and the compatibility is good, and further preferably.

The amount of the polymerizable monomer and/or oligomer used is relative to the component (A) and the component (B) from the viewpoints of improvement in surface hardenability, impartability of toughness, and workability in which viscosity is lowered. The total of 100 parts by weight (hereinafter, also referred to as a part) of the component D) is preferably from 1 to 200 parts, more preferably from 5 to 100 parts.

In order to improve the insulating property, an oligomer having a radical reactivity of a hydrophobic main chain may be added. For example, a di(meth)acrylate having a butadiene skeleton (trade name: BAC-45, manufactured by Osaka Organic Chemical Industry Co., Ltd.), an urethane urethane having a double A skeleton, and a ring having a double A skeleton may be mentioned. Oxy acrylate, polyester acrylate having a double A skeleton, respective hydrides, and the like.

In the curable composition of the present invention, a curing reaction other than the curing reaction by the polymerization of the vinyl group of the component (A), the component (B) and the component (D) can be used in combination. As an advantage of the combination hardening reaction, for example, when the (A) component, the (B) component, and the (D) component of the present invention are hardened by using a photoradical polymerization initiator as the component (C), the light is not irradiated. The shaded parts will harden. In this case, the shadow portion can be hardened by using a hardening reaction in combination.

In the case where a hardening reaction is used in combination, the terminal polymer having a (meth) acrylonitrile group at the molecular terminal of the (A) component of the present invention may be an epoxy group, an alkenyl group, or a hydrolyzate. A vinyl polymer of a mercaptoalkyl group. The introduction method of these functional groups is as follows.

[epoxy group]

A known method can be employed for introduction of an epoxy group into a vinyl polymer. For example, the method described in paragraphs [0039] to [0056] of JP-A-2000-154212 can be cited. Preferred examples are also described in this paragraph.

[alkenyl]

A known method can be employed as a method of introducing an alkenyl group capable of performing a hydrogenation reaction into the obtained ethylene-based polymer. For example, the method described in paragraphs [0042] to [0086] of JP-A-2004-059783 can be cited. Further, preferred examples are also described in this paragraph.

[hydrolyzable alkylene group]

A known method can be employed as a method of introducing a hydrolyzable alkylene group into the obtained ethylene-based polymer. For example, the method described in paragraphs [0076] to [0138] of JP-A-2000-191912 can be cited. Further, preferred examples are also described in this paragraph.

As a polymerization initiator or a polymerization catalyst in the case where a vinyl polymer having a terminal functional group of an epoxy group, an alkenyl group or a hydrolyzable alkylene group is used, the following may be used.

As a polymerization initiator or a polymerization catalyst in the case where the terminal functional group is an epoxy group-based ethylene-based polymer, for example, those described in paragraph [0059] of JP-A-2000-154212 can be used.

In the case of a vinyl polymer having a terminal functional group as an alkenyl group, a compound containing a hydroquinone group is preferably used in combination, and examples thereof include those described in JP-A-2004-059783 [0087] to [0091]. In order to promote the hydrogenation reaction of ruthenium, it is preferred to use a ruthenium hydrogenation catalyst in combination, which is described in the publication [0092].

In the case where the terminal functional group is a hydrolyzable alkylene group-containing vinyl polymer, a curing catalyst is preferred, and examples thereof include those described in paragraphs [0147] to [0150] of JP-A-2000-191912.

<antioxidant>

Various antioxidants can also be used as needed in the curable composition of the present invention. Examples of such antioxidants include amine-based antioxidants, hindered phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

Among these, a hindered phenol-based antioxidant is preferred in terms of less discoloration of the cured product.

Specific examples thereof include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, and mono (or di- or tri-) (α). -methylbenzyl)phenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6- Tributylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol ), 2,5-di-t-butyl hydroquinone, 2,5-di-third amyl hydroquinone, triethylene glycol-bis-[3-(3-tert-butyl- 5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] , 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylaniline)-1,3,5-three , pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-diethylidene bis[3-(3,5- Di-t-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, N,N '-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-phenylpropanamide), 3,5-di-t-butyl-4-hydroxy-benzylphosphonic acid-II Ethyl ester, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, bis(3,5-di-third Ethyl butyl-4-hydroxybenzylphosphonate) Calcium, tris-(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, 2,4-2,4-double [(octylthio)methyl] o-cresol, N, N'-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propanyl]anthracene, three (2, 4-di-t-butylphenyl)phosphite, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α - dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-third Butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriene Azole, 2-(3,5-di-third amyl-2-hydroxyphenyl) Benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)-benzotriazole, methyl-3-[3-tert-butyl-5-(2H-benzotrien) a condensate of oxazol-2-yl)-4-hydroxyphenyl]propionate-polyethylene glycol (molecular weight about 300), a hydroxyphenylbenzotriazole derivative, 2-(3,5-di- Tributyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-pentamethyl-4-piperidyl) ester, 2,4-di- Tributylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate or the like.

These hindered phenol-based antioxidants may be used singly or in combination of two or more. More preferably, the hindered phenol-based antioxidant has a molecular weight of 600 or more of tetrakis-[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl) in terms of improving heat resistance. Propionate] methane, tris-[N-(3,5-di-t-butyl-4-hydroxybenzyl)]isocyanurate, 1,3,5-trimethyl-2,4 ,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 3,9-bis{2-[3-(3-t-butyl-4-hydroxy-5-- Phenyl phenyl) propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxa[5,5]undecane. Further, the molecular weight can be measured using GC-MS or LC-MS.

The amount of the hindered phenol-based antioxidant to be used is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the total of the ethylene-based polymers (A) and (B). When the amount is less than 0.1 part by weight, the effect of improving heat resistance is small, and even if it exceeds 5 parts by weight, there is no significant difference and it is economically disadvantageous.

<<Manufacturing method of curable composition>>

The curable composition of the present invention can be prepared into a liquid type in which all the formulated components are pre-formulated and sealed, or can be prepared to select only the starting agent or the hardening catalyst or the crosslinking agent before the forming. A two-liquid type in which a starter or a curing catalyst or a crosslinking agent is mixed with a filler B, a plasticizer, a solvent, or the like, and a liquid B is mixed.

<<Cured material>>

The cured product of the present invention is obtained by curing the curable composition.

The method of curing the curable composition is not particularly limited.

When a thermal polymerization initiator is used in combination as a starter component, the curing temperature depends on the type of the thermal polymerization initiator, the component (A), the component (B), the component (D), and other additives. It is different, but it is usually preferably from 50 ° C to 250 ° C, more preferably from 70 ° C to 200 ° C.

Hardening can be hardened by irradiating light or an electron beam with an active energy ray source. The active energy ray source is not particularly limited, and examples thereof include a high pressure mercury lamp, a low pressure mercury lamp, an electron beam irradiation device, a halogen lamp, a light emitting diode, and a semiconductor laser depending on the nature of the photopolymerization initiator to be used. Metal halide lamps, etc. The hardening temperature is preferably 100 ° C or lower, more preferably 80 ° C or lower, and still more preferably 50 ° C or lower. In the case of hardening at 100 ° C or higher, the strain is increased due to the difference in linear expansion between the cured product and the substrate.

In the case where a redox initiator is used as the other initiator, the hardening temperature is preferably from -50 ° C to 250 ° C, more preferably from 0 ° C to 180 ° C.

<<Forming method>>

The molding method in the case where the curable composition of the present invention is used as a molded body is not particularly limited, and various molding methods which are generally used can be used. For example, casting molding, compression molding, transfer molding, injection molding, extrusion molding, rotational molding, hollow molding, hot molding, and the like can be mentioned. In particular, it is preferable to use autoforming, continuous, and excellent productivity, and it is preferable to use roll forming, calendering, extrusion molding, liquid injection molding, and injection molding.

<<Use>>

The curable composition and the cured product of the present invention are preferably used for electrical and electronic component materials in contact with the electrode metal, and are not particularly limited, and can be used for electrical insulating materials such as insulating coating materials for electric wires and cables, sealing materials, and the like. Adhesives, adhesives, conformal coatings, potting agents for electric and electronic applications, heat-dissipating materials, waterproof materials, anti-vibration/vibration/vibration-free materials, films, marine deck caulking, casting materials Or forming materials.

In the field of electrical and electronic components, it can be used for coatings, potting materials, gaskets, O-rings, belts, etc. Specific examples include a thick film resistor for high voltage, a circuit element of a hybrid circuit (Hybrid IC), an HIC (Hybrid Integrated Circuit), an electrically insulating element, a semiconductive element, and a conductive element. Coating materials for modules, printed circuits, ceramic substrates, diodes, buffers for transistors or wiring, semi-conductor components, or optical fibers for optical communication, transformer high voltage circuits, printed substrates, and variable High-voltage transformers for electrical resistance, electrical insulation components, semi-conductive components, conductive components, potting materials for solar cells or TV resilience transformers, heavy-duty components, weak electrical components, backside sealing of solar cells, electrical and electronic equipment Sealing materials for circuits and substrates, decorative materials for lighting fixtures, waterproof gaskets, anti-vibration rubbers, insect-proof gaskets, anti-vibration for sound absorbers, sound-absorbing and air-sealing materials, anti-drip caps for electric water heaters, Heating pad, electrode pad, safety valve diaphragm, hose for wine cooler, waterproof gasket, solenoid valve, steam oven and waterproof lining for rice cooker , for water tank gaskets, suction valves, water-filled gaskets, connecting hoses, belts, insulation heating gaskets, steam outlet seals, oil-impregnated gaskets for combustion equipment, O-rings, drainage liners, plus Pressure pipe, air supply pipe, delivery, suction pad, anti-vibration rubber, oil inlet gasket, oil gauge gasket, oil supply pipe, diaphragm valve, air supply pipe, speaker pad for audio equipment, speaker edge Rubber components such as sides, turntables, belts, pulleys, etc. Also, it can be used as an adhesive for Brown tube wedges, necks, electrical insulation elements, semi-conductive elements or conductive elements, maintenance materials for wire coating, insulation sealing materials for wire joint components, OA machines (Office Automation Equipment, office automation) Equipment) Rolls, ink wiping paper, vibration absorbers, gels, and the like.

[Examples]

Hereinafter, the present invention will be described in more detail by way of specific examples, but the invention is not limited to the following examples.

Further, in the following examples, "number average molecular weight" and "molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)" are determined by a standard polystyrene conversion algorithm using gel permeation chromatography (GPC). Calculated. Among them, those filled with a polystyrene crosslinked gel (shodex GPC K-804 and K-802.5; manufactured by Showa Denko Co., Ltd.) were used as a GPC column, and chloroform was used as a GPC solvent.

In the following examples, "the number of (meth)acrylonitrile groups introduced into one molecule of the polymer" was calculated from the number average molecular weight determined by ¹ H-NMR analysis and GPC.

(Wherein, ¹ H-NMR system manufactured by Bruker's ASX-400, at 23 ℃ measured using deuterated chloroform as a solvent)

(viscosity)

The viscosity of the obtained polymer and the mixing portion was measured in accordance with JIS K 7117-2 cone-plate system using an E-type viscometer manufactured by Toki Sangyo Co., Ltd. at a measurement temperature of 23 °C.

(insulation value)

The insulation value was measured by using a super insulation meter of model SM-8213 manufactured by HIOKI Co., Ltd., and the measured value after 30 seconds of DC (direct current) at 100 V was taken as an insulation value.

(electrode discoloration)

After the electric high temperature and high humidity test was conducted, the comb substrate was visually observed. The comb-shaped substrate has an anode, a cathode, and an electrode without a charge, and the difference between the electrode metal and the discoloration is ○, and the difference between the electrode metal and the discoloration is ×.

(mechanical properties)

According to JIS K 6251, the cured product was cut into a size of 2 mm thick and No. 3 dumbbell, and measured under the conditions of a tensile speed of 200 mm/min and 23 ° C × 55% RH. In the tensile test, an autograph AG-2000A manufactured by Shimadzu was used.

(Powered high temperature and high humidity test)

The moisture resistance test was applied according to the voltage of 8.7.4 of JIS K 3197, and the test was performed using a comb substrate. The conductor of the comb substrate was made of copper, the base material was made of epoxy glass (FR4), the conductor width was set to 0.318 mm, the conductor spacing was set to 0.318 mm, and the overlap margin was set to 15.75 mm. After the coating film having a thickness of 50 μm was formed on the comb substrate, the wires were welded. The wire is a coated wire (fluororesin coated wire, 1.2 mm Φ, rated 600 V) that can be used under high temperature and high humidity conditions.

A comb-shaped substrate is arranged in the constant temperature and humidity machine, and the wire is extended outside the constant temperature and humidity machine to perform rated energization. After a certain period of time, the comb substrate was measured for insulation at the end of the wire extending outside the constant temperature and humidity machine under high temperature and high humidity. The conditions of the energized high temperature and high humidity test were set to DC 50 V, 85 ° C, 85% RH, and 500 hours.

(UV curing)

An H valve of model LH6 manufactured by Fusion UV Systems Japan Co., Ltd. was used. The ultraviolet curing conditions were set to 1500 mW/cm ² and 3000 mJ/cm ² .

<Production Example 1: Synthesis of poly(n-butyl acrylate) having an acryl fluorenyl group at both ends>

100 parts of n-butyl acrylate was deoxidized. The inside of the reaction vessel was deoxidized, and 0.17 parts of cuprous bromide, 20 parts of n-butyl acrylate, 4.4 parts of acetonitrile, and 3.5 parts of diethyl 2,5-dibromoadipate were added and mixed at 70 ° C. Then, 0.010 parts of pentamethyldiethylenetriamine (hereinafter, abbreviated as triamine) was added to start a polymerization reaction. 80 parts of the monomer mixture was successively added to allow the polymerization to proceed.

In the middle of the polymerization, the triamine is appropriately added to adjust the polymerization rate, and the internal temperature is adjusted to about 80 ° C to about 90 ° C to carry out the polymerization. When the monomer conversion rate (polymerization rate) is about 95% or more, the oxygen-nitrogen mixed gas is introduced into the gas phase of the reaction vessel, and the internal temperature is maintained at about 80 ° C to about 90 ° C while heating and stirring. The volatile component was removed under reduced pressure and concentrated. It was diluted with butyl acetate, a filter aid was added and filtered. An adsorbent (Kyowaad 700SEN, Kyowaad 500SH, manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the filtrate, and the mixture was heated and stirred, and then filtered to concentrate the filtrate. Dissolve it in N,N-dimethylacetamide, add potassium acrylate (about 2 molar equivalents relative to the terminal Br group), heat stabilizer (H-TEMPO: 4-hydroxy-2, 2, 6 , 6-tetramethylpiperidine-n-hydroxyl ester), adsorbent (Kyowaad 700SEN), and heated and stirred at about 70 °C. The volatile component was distilled off under reduced pressure, and then diluted with butyl acetate, and filtered, and filtered. The filtrate was concentrated to obtain "Polymer II" having an acrylonitrile group at both ends.

The "polymer I" had a number average molecular weight of 12,000 and a molecular weight distribution of 1.2, and the average number of acrylonitrile groups per molecule of the polymer introduced was 1.8.

<Production Example 2: Synthesis of poly(n-butyl acrylate/2-ethylhexyl acrylate) having an acryl fluorenyl group at both ends)>

A monomer mixture comprising 2 parts of n-butyl acrylate and 98 parts of 2-ethylhexyl acrylate was deoxygenated. The inside of the reaction vessel was deoxidized, and 0.29 parts of cuprous bromide, 20 parts of the monomer mixture, 8.9 parts of acetonitrile, and 2.5 parts of diethyl 2,5-dibromoadipate were added, and the mixture was mixed at 80 ° C. 0.014 parts of pentamethyldiethylenetriamine (hereinafter, abbreviated as triamine) was started, and polymerization was started. 80 parts of the monomer mixture was successively added to allow the polymerization to proceed. In the middle of the polymerization, the triamine is appropriately added to adjust the polymerization rate, and the internal temperature is adjusted to about 80 ° C to about 90 ° C to carry out the polymerization. When the monomer conversion (polymerization rate) is about 95% or more, the oxygen-nitrogen mixed gas is introduced into the gas phase of the reaction vessel, and the internal temperature is maintained at about 80 ° C to about 90 ° C while heating and stirring. The volatile component was removed under reduced pressure and concentrated. It was diluted with butyl acetate, a filter aid was added and filtered. An adsorbent (Kyowaad 700SEN, Kyowaad 500SH manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the filtrate, and the mixture was heated and stirred, and then filtered to concentrate the filtrate. Dissolve it in N,N-dimethylacetamide, add potassium acrylate (about 2 molar equivalents relative to the terminal Br group), heat stabilizer (H-TEMPO: 4-hydroxy-2, 2, 6 , 6-tetramethylpiperidine-n-hydroxyl ester), adsorbent (Kyowaad 700SEN), and heated and stirred at about 70 °C. The volatile component was distilled off under reduced pressure, diluted with butyl acetate, and filtered, and filtered. The filtrate was concentrated to obtain "Polymer II" having an acrylonitrile group at both ends.

The "polymer II" had a number average molecular weight of 13,500 and a molecular weight distribution of 1.3, and the average number of acrylonitrile groups per molecule of the polymer was 1.6.

<Examples 1 to 9, Comparative Examples 1 to 9, and Reference Examples 1 to 2>

Explain the method of deployment. Adding an antioxidant to "Polymer I" or "Polymer II" of the component (A) obtained in Production Example 1 or 2, and heating and mixing at 120 ° C for 2 hours to dissolve the antioxidant in "Polymer I" or In Polymer II. After cooling to 50 ° C or less, the component (B), the component (D), the component (C), and other components were added, and the mixture was homogenized by a stirring defoaming device (manufactured by Thinky Co., Ltd., ARE-250). In addition, the component (C) was prepared by dissolving DAROCUR 1173 (manufactured by Ciba Japan) and IRGACURE 819 (manufactured by Ciba Japan) in advance by heating. The blending amount ("parts by weight") is shown in Tables 1 to 3. Further, in the table, (B) component Light acrylate DCP-A represents dimethylol tricyclodecane diacrylate, V#260 represents 1,9-nonanediol diacrylate, and (D) component ISTA represents Isostearyl acrylate, IBXA means isobornyl acrylate, FA-513A means dicyclopentanyl acrylate, and Naugard 445 of antioxidant means 4,4'-bis(α,α'-dimethylbenzyl)diphenyl The base amine, IRGANOX 1010, represents tetrakis-[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane.

Next, the ultraviolet curing method will be described. The preparation is applied to a comb-shaped substrate to a thickness of 50 μm, and the mold is allowed to flow into the mold frame so as to have a thickness of about 2 mm. The ultraviolet irradiation device (manufactured by Fusion UV Systems Japan, model LH6, H valve), hardened at 1500 mW/cm ² and 3000 mJ/cm ² . The test results are shown in Tables 1-3.

In Examples 1 to 5 in which the component (B) was contained in an amount of 25% by weight or more and 45% by weight or less based on 100% by weight of the total of the components (A) and (B), the electrode metal after the high-temperature and high-humidity test was not found. Discoloration. When the component (B) was less than 25% by weight, the discoloration between the electrode metals after the high-temperature and high-humidity test was found. When it contains more than 45% by weight of the component (B), it is a hard cured material and cannot be cut into a dumbbell. Such a hard cured product tends to peel off the end of the coating film from the substrate. Furthermore, the O.R. value of the insulation value indicates that it is out of range.

In addition, the total of the component (B) and the component (D) is 25% by weight or more and 65% by weight or less based on 100% by weight of the total of the component (A), the component (B), and the component (D), and (B) In Examples 6 to 9 in which the composition was 5% by weight or more, discoloration between the electrode metals after the high-temperature and high-humidity test was not observed. Also, the elongation is longer than in the case of using only the component (B). When only the component (D) was used (Comparative Examples 6 and 7), discoloration between the electrode metals was observed after the high-temperature and high-humidity test. When the total of the components (B) and (D) was less than 25% by weight (Comparative Example 8), the discoloration between the electrode metals after the high-temperature and high-humidity test was found. When the butyl acrylate having a carbon number of 6 or less (Comparative Example 9) was used, the discoloration between the electrode metals after the high-temperature and high-humidity test was found. When the component (A) is not used and the total of the component (B) and the component (D) is more than 65% by weight (Comparative Example 10), it is a hard cured product and cannot be cut into a dumbbell. Such a hard cured product tends to peel off the end of the coating film from the substrate.

Table 3 shows the results of conducting the energization test in the same manner as in the comb-shaped substrate of Comparative Example 1 and Table 3 of Table 1 at 85 ° C and 10% RH. In Reference Examples 1 and 2, there was no discoloration between the electrode metals, and it was considered that the electrode was discolored when the humidity was high. It is considered that by using the component (B) and the component (D) of the present invention, the moisture absorption resistance of the coating film can be improved and the discoloration of the electrode can be improved.

[Industrial availability]

The curable composition of the present invention has low viscosity and can be hard-cured, and the cured product has excellent heat resistance, weather resistance, oil resistance, compression set, mechanical properties, and the like derived from the ethylene-based polymer, and the moisture absorption resistance is improved. Therefore, it is preferably used for electrical and electronic component materials, electrical insulating materials, sealing materials, adhesives, adhesives, potting agents, heat dissipating materials, waterproof materials, anti-vibration/vibration/vibration-free materials that require moisture absorption resistance, Film, ship deck interstitial materials, casting materials, coating materials, forming materials, etc.

Claims (17)

A composition for electrical and electronic component materials, comprising: (A) having at least one or more formulas (1): -OC(O)C(R ^a )=CH ₂ per molecule at the molecular end (1) (wherein, R ^a represents ^a vinyl polymer represented by a hydrogen atom or an organic group having 1 to 20 carbon atoms), and (B) has a formula (2): R ^b -(OC(O)C(R ^a )=CH ₂ ) _n (2) (wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ^b represents an organic group having 6 to 20 carbon atoms; n represents a vinyl monomer of a (meth)acrylinyl group represented by an integer of 2 to 6, and (C) a starter; and 100 weights based on the total of the components (A) and (B) % contains 25% by weight or more and 45% by weight or less of the component (B). A composition for electrical and electronic component materials, comprising: (A) having at least one or more formulas (1): -OC(O)C(R ^a )=CH ₂ (1) per molecule at the molecular end ( In the formula, R ^a represents ^a (meth)acryloyl group-based vinyl polymer represented by a hydrogen atom or an organic group having 1 to 20 carbon atoms, and (B) has a formula (2): R ^b - ( OC(O)C(R ^a )=CH ₂ ) _n (2) (wherein R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, R ^b represents an organic group having 6 to 20 carbon atoms, and n represents a (meth)acryloyl group-based vinyl monomer represented by an integer of 2 to 6, and (D) having the formula (3): R ^c -OC(O)C(R ^a )=CH ₂ ( 3) (wherein, R ^a represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and R ^c represents an organic group having 6 to 20 carbon atoms), and a vinyl monomer of a (meth)acrylonyl group represented by a group And (C) the initiator; and the total of the component (B) and the component (D) is 100% by weight or more, and the total of the components (B) and (D) is 25% by weight or more, and 65 parts by weight. It is 5% by weight or less and contains 5% by weight or more of the component (B). The composition for electrical and electronic component materials according to claim 2, wherein the total of the components (B) and (D) is 30% by weight based on 100% by weight of the total of the components (A), (B) and (D). It is a weight% or more, 55% by weight or less, and contains 15 weight% or more of (B) component. The composition for electrical and electronic component materials of claim 1, wherein the amount of the component (C) is 0.001 to 10 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (D). The composition for electrical and electronic component materials of claim 2, wherein the amount of the component (C) is 0.001 to 10 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (D). The composition for electrical and electronic component materials of claim 3, wherein the amount of the component (C) is 0.001 to 10 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (D). The composition for electrical and electronic component materials according to any one of claims 1 to 6, wherein the main chain of the component (A) is obtained by polymerizing an acrylate monomer. Made. The composition for electrical and electronic component materials according to any one of claims 1 to 6, wherein the main chain of the component (A) is produced by a living radical polymerization method. The composition for electrical and electronic component materials according to claim 8, wherein the main chain of the component (A) is produced by atom transfer radical polymerization. The composition for electrical and electronic component materials according to any one of claims 1 to 6, wherein the main chain of the component (A) is produced by polymerization of a vinyl monomer using a chain transfer agent. The composition for electrical and electronic component materials according to any one of claims 1 to 6, wherein the component (A) has a number average molecular weight of 3,000 or more. The composition for electrical and electronic component materials according to any one of claims 1 to 6, wherein the ratio of the weight average molecular weight to the number average molecular weight measured by gel permeation chromatography of the ethylene-based polymer of the component (A) is not Up to 1.8. The composition for electrical and electronic component materials according to any one of claims 1 to 6, wherein the component (B) is a vinyl monomer having two (meth)acrylonyl groups in one molecule. The composition for electrical and electronic component materials according to any one of claims 1 to 6, wherein the component (C) is a photoradical initiator. A composition for an electric or electronic component material which is in contact with an electrode metal according to any one of claims 1 to 14. An electrical or electronic component material that is as claimed in claims 1 to 15 A composition obtained by hardening a composition for electrical and electronic component materials. A cured product obtained by hardening a composition for an electric or electronic component material according to any one of claims 1 to 15 by an active energy ray or heat.